Di-ortho-substituted di-meta-halogenated para-halomethylphenols

ABSTRACT

Included is a process to prepare a 4-HALOmethyl-3,5-dihalo-2,6-disubstitutedphenol from a 4-methyl(substituted)phenol and a HALOgenating agent, in an aprotic organic diluent. The process is highly selective and efficient. For example, high purity 4-bromomethyl-3,5-dibromo-2,6-dimethylphenol can be prepared from 2,4,6-trimethylphenol and bromine, in bromochloromethane at high conversion.

FIELD

This invention concerns halogenated phenols, with a process to preparethem. The halogenated phenols are useful flame retardants, fungicidesand monomers.

BACKGROUND

Halomethylation of aromatics is a well established reaction. However,halomethylation of phenols is generally not a selective process. Ingeneral, it is difficult to obtain monomeric chloromethylated products.See, G. A. Olah, Friedel-Crafts and Related Reactions, Vol. II, Part 2,pp. 701-11, 1964. Halogenation of alkylphenols is normally accompaniedby side-reactions. V. V. Ershov, A. A. Volodkin & G. N. Bogdanov,Russion Chemical Reviews, 32, 75-93 (1963). Furthermore,bromomethylation, in general, affords lower yields thanchloromethylation, ibid., pp. 734-735.

The preparation of a halogenated phenol such as 4-bromomethyl-3,5-dibromo-2, 6-dimethylphenol (tribromomesitol) can involve thefollowing sequence: bromination of 2, 4, 6-trimethylphenol (mesitol)with 2 moles of bromine in acetic acid to prepare 3, 5-dibromo-2, 4,6-trimethylphenol (dibromometisol) which is isolated by precipitationwith water. K. Auwers & F. Rapp, Ann., 302, 153-71 (1898) and O.Jacobsen, Ann., 195, 265-92 (1879); the dibromomesit 1 is brominated inacetic acid sodium acetate buffer at low temperatures to afford anintermediate, 3, 4, 5-tribromo-2, 4, 6-trimethyl-2, 5-cyclohexadienone,which is isolated by fast precipitation with water and filtration; thissolid slowly rearranges to tribromomesitol at room temperature, morequickly at higher temperatures. K. Fries & E. Brandes, Ann., 542, 48-77(1939). This procedure to prepare tribromomesitol is complex and notindustrially viable.

A more direct method of preparation of tribromomesitol involves thereaction of mesitol in glacial acetic acid with an excess of bromine,using 10.6 moles of bromine per mole of mesitol. The yields are 66percent and the product isolation is difficult. K. Auwers and H.Allendorff, Ann., 302, 76-98 (1898). This procedure is not industriallyviable either.

Chlorination of 3, 5-dichloro-2, 4, 6-trimethylphenol in trifluoroaoeticacid is known to produce 3, 4, 5-trichloro-2, 4, 6-trimethyl-2,5-cyclohexadienone or 3, 5, 6-trichloro-2, 4, 6-trimethyl-2,4-cyclohexadienone. Antinori et al., J. Chem. Soc. (B), 373-77 (1969).

SUMMARY

The invention is a process for preparing a 4-HALOmethyl-3, 5-dihalo-2,6-disubstituted phenol comprising contacting a4-methyl(substituted)phenol with a HALOgenating agent, in an aproticorganic diluent, under conditions whereby the 4-HALOmethyl-3,5-dihalo-2, 6-disubstitutedphenol is prepared. The process is simple,highly selective and highly efficient. Characteristically, in general,the process requires no light nor the presence of base, and it can berun under moderate temperatures. The 4-HALOmethyl-3, 5-dihalo-2,6-disubstitutedphenols are useful flame retardants, fungicides andmonomer precursors for phenolic resins and engineering thermoplastics.

ILLUSTRATIVE EMBODIMENTS

Herein, the (exclusively upper case) syllabic "HALO" refers to a halogenselected from the group consisting of chlorine and bromine. "Halo"refers to any halogen, preferably selected from the group consisting offluorine, chlorine and bromine. Thus, for example, a bromo moiety isboth "HALO" and "halo": whereas a fluoro moiety is only "halo"

The 4-HALOmethyl-3, 5-dihalo-2, 6-disubstitutedphenols are a type ofhalogenated phenol. The 4-HALOmethyl-3, 5-dihalo-2,6-disubstitutedphenols include compounds of the general formula ##STR1##wherein

Q is separately at each occurrence alkyl (with at most secondary (2° )carbon bonded directly to the phenol ring) or generallyinertly-substituted alkyl, each preferably maximally of about 12 carbons(C₁₋₁₂), more preferably the alkyl and most preferably methyl;

X is separately at each occurrence one of the halo moieties, morepreferably HALO and most preferably Br; and

X' is HALO and preferably Br.

The most preferred of the 4-HALOmethyl-3, 5-dihalo-2,6-disubstitutedphenols is 4-bromomethyl3, 5-dibromo-2, 6-dimethylphenol.

The 4-methyl(substituted)phenols include compounds of the generalformula ##STR2## wherein Q is as defined herein, and each Q generallycorresponds to each Q of the compounds of the formula (I); and

Q' is separately at each occurrence hydro (H) or X (as defined herein)and preferably H.

The most preferred of the 4-methyl(substituted)phenols is 2, 4,6-trimethylphenol (mesitol).

The generally inertly-substituted alkyl (Q) moieties are thosesubstituted alkyl moieties which do not, in general, interfere with theprocess for preparing the corresponding 4-HALOmethyl-3, 5-dihalo-2,6-disubstitutedphenol. For example, the generally inertly-substitutedalkyl moiety can be an alkyl moiety which is substituted with a moietysuch as an ether moiety or a halo moiety.

The 4-methyl(substituted)phenols can be commercially obtained orprepared by known procedures or by the process herein, which can beemployed to prepare the 4-methyl(substituted)phenols of the formula(II), for example, with the desired halo Q' moiety. The4-methyl(substituted)phenols, for example, of the formula (II) with eachQ' hydro, are commercially available (for example, 2, 4,6-trimethylphenol) or they can be prepared by known procedures, forexample, by the processes disclosed by Norton et al., U.S. Pat. No.2,841,623 (1958); Walts et al., U.S. Pat. No. 3,360,573 (1967); VanSorge, U.S. Pat. Nos. 3,751,488 (1973) and 3,764,630 (1973); Suzuki etal., U.S. Pat. Nos. 3,899,540 (1975) and 3,976,702 (1976) (eachincorporated herein by reference).

The HALOgenating agent is a means for imparting a HALO (Cl; Br) moietyto (at least the 4-methyl moiety of) the 4-methyl(substituted)phenol toprepare the 4-HALOmethyl-3, 5-dihalo-2, 6-disubstitutedphenol. Thus, theHALOgenating agent is a suitable source of HALO moiety. The HALOgenatingagent can include molecular HALOgens which include the elementalHALOgens, elemental bromine (Br₂) and elemental chlorine (Cl₂), andcompounds such as, for example, bromine chloride. The HALOgenating agentcan be an organic HALOgenating agent such as, for example,N-bromosuccinimide (a suitable source of the bromo moiety) and sulfurylchloride (a suitable source of the chloro moiety).

Preferably, the HALOgenating agent is the molecular HALOgen. Preferably,the molecular HALOgen is elemental bromine.

The aprotic organic diluent is generally inert. Thus, the aproticorganic diluent does not, in general, interfere with the process toprepare the 4-HALOmethyl-3, 5-dihalo-2, 6-disubstitutedphenol. Ingeneral, the aprotric organic diluent is a liquid under the conditionsof the process and preferably is a liquid at about room temperature (25°C). The aprotic organic diluent is preferably considered generally suchas a liquid solvent. The aprotic organic diluent can thus includediluents such as alkanes such as, for example, cyclohexane; haloalkanessuch as, for example, dichlorofluoromethane, methylene chloride,chloroform, carbon tetrachloride, bromochloromethane, ethylenedichloride; and halogenated aromatics such as, for example,ortho-dichlorobenzene. However, the heterocyclic ether tetrahydrofuran,when employed as the sole aprotic organic diluent, typically does notenhance the higher efficiencies of the process, and it is thus notpreferred.

Preferred of the aprotic organic diluents are the haloalkanes. Mostpreferably, the haloalkane is bromochloromethane.

In the practice of the invention, the 4-methyl(substituted)phenol iscontacted with the HALOgenating agent. Conditions are those sufficientto prepare the 4-HALOmethyl-3, 5-dihalo-2, 6-disubstitutedphenol.

Amounts of the HALOgenating agent thus required can, in general, rangefrom about one atomic equivalent to about ten atomic equivalents permole of the 4-methyl(substituted)phenol reactant. The atomic equivalentsare based on the equivalents of HALO moiety generally available from theHALOgenating agent for imparting to the 4-methyl(substituted)phenol toprepare the 4-HALOmethyl-3, 5-dihalo-2, 6-disubstitutedphenol. Forexample, one mole of the molecular HALOgen elemental bromine generallycontains one atomic equivalent of bromo moiety available for theimparting to the 4-methyl(substituted)phenol. Typically, upon theHALOgenation, a by-product of hydrogen chloride or bromide is produced.

In general, the ratio of the atomic equivalents of the HALOgenatingagent employed per mole of the 4-methyl(substituted)phenol (converted toany of the halogenated phenols) can be from about 1:1 to about 7:1, andwith each Q' moiety halo, for example, to about 5:1. Preferably, withthe Q' moiety of the 4-methyl(substituted) phenol each hydro, the ratioof the atomic equivalents of the halogenating agent employed per mole ofthe 4-methyl(substituted)phenol (converted to any of the halogenatedphenols) is from about 3:1 to about 5:1 and most preferably from about3.2:1 to about 4:1. Thus, it is most preferred that at least about oneatomic equivalent of the HALOgenating agent or slightly more is employedper molar equivalent of the 4-methyl moiety of the4-methyl(substituted)phenol.

A halogenating agent other than the HALOgenating agent may be employedto impart other halo moieties, for example, to the 3 or 5 positions ofthe ring with hydro for a Q' moiety. The other halogenating agent canthus be a fluorinating agent such as, for example, perchloryl fluoride(ClO₃ F). The use of the HALOgenating agent is preferred.

Amounts of the aprotic organic diluent thus required can, in general,vary over a wide range. Preferably, the amount is sufficient to preparea slurry or solution with the reactants or products. Preferably, theratio of moles of aprotic organic diluent employed per mole of the4-methyl(substituted)phenol is from about 5:1 to 1000:1 and morepreferably from 10:1 to 50:1. The aprotic organic diluent can be used toinitially dilute either the 4-methyl(substituted)phenol or halogenatingagent, for example, the HALOgenating agent, or a plurality of them.

Temperatures employed can generally range from cool to elevatedtemperatures. The cool temperatures include temperatures such as aboutroom temperature (25° C.) or below to temperatures such as to minus 120°C. and preferably to about 0° C. The elevated temperatures includetemperatures of 30° C. or above, preferably to 100° C. and morepreferably from about 35° C. to about 85° C.

For the most part, the cool temperatures are preferably employed ininitial stages such as which can impart appropriate halo moieties to the3 or 5 positions of the ring. Also, the cool temperatures are preferablyemployed throughout with the HALOgenating agent such as elementalchlorine (or even halogenating agent such as perchloryl fluoride). And,the elevated temperatures are preferably employed thereafter especially,for example, with the HALOgenating agent such as elemental bromine. Ingeneral, the higher the temperature is, the faster the rate of theprocess becomes.

Pressures employed can, in general, vary over a wide range. The pressureemployed can be supra- or subatmospheric. However, ambient pressure isgenerally preferred during the preparation.

Time (duration) of the process can, in general, vary over a broad range,for example, from a few minutes to several days. Preferably, the time ofcarrying out the process is from about half an hour to about ten hoursand more preferably from about one hour to about seven hours. Mostpreferably, the time employed is from about two to about five hours,especially with the HALOgenating agent such as elemental bromine becausetypically greater than about ninety percent of the4-methyl(substituted)phenols are converted to the appropriate productwithin the span of this latter time period. Shorter times can typicallybe employed when employing more of the HALOgenating agent.

The 4-HALOmethyl-3, 5-dihalo-2, 6-disubstitutedphenols can often beemployed as thus prepared, especially such as with, for example, fromabout 95 percent to 99 percent (by weight) purity, or can be furtherpurified by known methods. Preferably, purification involvesrecrystallization such as, for example, from toluene, carbontetrachloride, methylene chloride or bromochloromethane.

In general, the process is highly selective and efficient. Preferably,the conversion of the 4-methyl(substituted)phenol to any (more)halogenated phenol (converted product) is thus 50 percent (by weight) orgreater, and can be about 65 percent or greater, even 80 percent orgreater. Selectivity of the thus converted product to the4-HALOmethyl-3, 5-dihalo-2, 6-disubstitutedphenol itself can thus be ashigh as 80 percent (by weight) of the converted product or above, evenas high as 90 percent of the converted product or above, more preferablyabout 95 percent of the converted product or above. Selectivity of theisolated product as high as 98 percent (by weight) or above, including99 percent, can be thus obtained even without recrystallization. Thus,the yield of the 4-HALOmethyl-3, 5-dihalo-2, 6-disubstitutedphenol (ingeneral: decimal value of the conversion multiplied by decimal value ofthe selectivity, multiplied by 100 percent) can be high. Preferably, theyield is thus 40 percent (by weight) or above, more preferably 50percent or above and can be about 65 percent or above. The yield of the4-HALOmethyl-3, 5-dihalo-2, 6-disubstitutedphenol can thus even be ashigh as about 75 percent, even 80 percent, or above, by weight.

The following preferred sequence generally illustrates the overallprocess: ##STR3## wherein Q, X and X' are as defined herein;

the 4-methyl(substituted)phenol of the step (A) is contacted with thehalogenating agent, preferably the HALOgenating agent, liberatingcorresponding hydrogen halide; and

the 4-methyl(substituted)phenol of the step (B) is contacted with theHALOgenating agent, liberating corresponding hydrogen halide.

The 4-methyl(substituted)phenol prepared in the step (A) can beisolated, if desired, purified and even reacted later in time. The step(B) alone is, of course, within the scope of the invention (with Q' ofthe 4-methyl(substituted)phenol of the formula (II) being X).Preferably, the process is carried out in the same reaction vessel bycarrying out both of the steps (A) and (B) without special isolation ofany halogenated intermediate 4-methyl(substituted)phenol and generallywithout intermission of a significant time between the steps (A) and(B).

SPECIFIC EMBODIMENTS

The following examples further illustrate the invention. Parts andpercentages are by weight unless specified otherwise.

EXAMPLE 1 Preparation of 4-Bromomethyl-3, 5-dibromo-2, 6-dimethylphenol(Tribromomesitol)

A 136.2-g portion of 2, 4, 6-trimethylphenol (1.0 mole) (93 percentpure; General Electric) is dissolved in 2.0 liters of carbontetrachloride. Using a water bath for cooling, 205 ml of bromine (4.0moles) is added at 20° C. -26° C. over a period of 15 minutes. Hydrogenbromide gas is given off during the bromine addition, and a slurry of 3,5-dibromo-2, 4, 6-trimethylphenol is obtained.

The temperature is increased to 70° C. -75° C., and a solution isobtained. The solution is held at 70° C. -75° C. for 3 hours. Theunreacted bromine is removed by distillation with the aid of 1 liter ofcarbon tetrachloride. When 1 liter of solvent remains with the product,the solution is cooled to 25° C. The light brown solid which is obtainedis filtered and is dried under vacuum for 5 hours. A yield of 250 g (67percent) is obtained, which analysis by gas chromatography shows to be97 percent tribromomesitol and 3 percent dibromomesitol. The product hasa melting point of 144° C. -146° C. and has the following proton nuclearmagnetic resonance spectrum (CDCl₃), δ: 2.30 (s, 6H), 4.90 (s, 2H),which is consistent with the structure of the product.

EXAMPLE 2 Process Variations: Amount of HALOgenating Agent; Time

A 230-ml portion of bromine (4.5 moles) is added to 1.0 mole of 2, 4,6-trimethylphenol (93 percent pure; General Electric) in 2 liters ofcarbon tetrachloride; the refluxing period is 2 hours, and 260 g ofproduct is obtained (70 percent conversion), otherwise following thework-up of Example 1. The crude solid is analyzed as 99 percenttribromomesitol.

EXAMPLE 3 Process Variations: Aprotic Organic Diluents; Temperatures

A 13.6-g portion of 2, 4, 6-trimethylphenol (0.1 mole) (99 percent pure;Aldrich Chemical Co.) is dissolved in 200 ml of the following aproticorganic diluent (Diluent), and 20.5 ml of bromine (0.4 moles) is addedat 19° C. -23° C. using a water bath for cooling. A solid forms which isslurried, and the slurry is heated at the following reflux temperature(Temp) for 2 hours. The excess bromine is then removed by distillationwith the aid of 500 ml additional of the listed aprotic organic diluent,and the remaining diluent is removed under vacuum. The product isweighed and is analyzed by gas chromatography for the conversion andselectivity of the product to 4-bromomethyl-3, 5-dibromo-2,6-dimethylphenol, and the yield is calculated. The following isobserved.

    ______________________________________                                                       °C.                                                                             grams of                                                                              %        %                                    Run   Diluent  Temp     Conversion                                                                            Selectivity                                                                            Yield                                ______________________________________                                        A     cyclo-   76-78    34.0    63       63                                         hexane                                                                  B     CH.sub.2 Cl.sub.2                                                                      38-39    32.9    33       33                                   C     CHCl.sub.3                                                                             59-60    35.5    61       61                                   D     CCl.sub.4                                                                              71-74    37.2    83       83                                   E     (CH.sub.2 Cl).sub.2                                                                    79-81    38.7    98       98                                   F     CH.sub.2 BrCl                                                                          66-68    37.3    91       91                                   ______________________________________                                    

EXAMPLE 4 Pilot Scale Production

Two batches of high purity 4-bromomethyl-3, 5-dibromo-2,6-dimethylphenol are efficiently prepared in a 100-gallon (376-liter)Pfaudler glass-lined reactor by the following procedures A and B. Ofthese, the procedure of Run B is preferred.

A. Preparation

To start, 800 pounds (360 kg) of bromochloromethane is pumped into thereactor for each run. Next, 90° C. (melted) mesitol is vacuum loaded,84.5 pounds (38.3 kg) in Run A and 113 pounds (51.3 kg) in Run B.Bromine, 347.5 pounds (157.6 kg) in Run A and 437 pounds (198 kg) in RunB, is steadily added over a period of time, 1 hour and 18 minutes in RunA and 2 hours and 8 minutes in Run B, with the reactor stirrer at125-130 rotations per minute (rpm). Each procedure starts out at 30° C.and is somewhat above 60° C. upon completion of the bromine addition.During each bromine addition, heat is applied to offset the cold (5° C.-10° C.) reflux. Approximately 2/3 of the way through each bromineaddition, the temperature is 50° C., and the batch briefly thickens, andthe air motor stirrer of the reactor drops 6 rpm in Run A and 12 rpm inRun B. From this point on, the reaction slows considerably.

The cook upon completion of each bromine addition lasts a period oftime, 71/2 hours in Run A and 81/3 hours in Run B. Each cook starts atabout 68° C., and the temperature upon completion of each cook is about73° C., and each batch is heated to keep the temperatures generallywithin this range, and maximum applied heating is carried out whilekeeping the reactor pressure less than 2 psig (a gauge pressure of lessthan about 26 kPa) and condenser reflux less than 10° C. by setting thewater jacket temperature of the reflux condenser to 3° C.

Upon completion of each reaction, the reactor jacket is set at 60° C.and propylene is sparged in, 9 pounds (4 kg) in Run A and about 41/2pounds (2 kg) in Run B. Neutralization completion is indicated by lossof exotherm temperature and sudden disappearance of colored brominevapors in the reactor headspace.

Upon completion of the neutralization, each product mixture is allowedto cool slowly, no faster than 20° C. per hour. Product precipitationoccurs at about 28° C. -30° C. in Run A and about 35° C. in Run B. Eachbatch is cooled to 2° C. -4° C. and is dropped into a large batch filterand is next manually transferred to a 20-inch (about 50.8 cm)centrifuge, whereupon completion of centrifugation, solvent remains, 13percent in Run A and 21.7 percent in Run B. A tan product results, 113pounds (51.3 kg) in Run A (49 percent yield) and 182 pounds (82.6 kg) inRun B (59 percent yield).

B. Recrystallization

The centrifuged product of Runs A and B are combined, and in a clean100-gallon Pfaudler reactor, 278 pounds (126 kg) of dry solids fromuniformly mixing Runs A and B is slurried in 75 gallons (280 liters) ofmethylene chloride. The mixture is heated to 60° C. The pressure is 15psig (a gauge pressure of about 103 kPa). Dissolution occurs near 50°C., and the stirring is maintained at 100 rpm during the heating. Thesolution is cooled at 20° C. per hour. Crystallization occurs at 44° C.,whereupon the stirrer is slowed to 60 rpm. Upon cooling to 20° C.,refrigeration is applied to the reactor overnight. The slurry iscentrifuged at -3° C. (minus 3° C.) and is dried under vacuum in a2-foot (61-cm) rotary cone Pfaudler dryer in 3 loads. The product is 212pounds (96.2 kg) of a white, fluffy solid (76 percent recrystallizationyield) which melts at 146° C. -147° C. and is analyzed by gaschromatography to be more than 99 percent pure 4-bromomethyl-3,5-dibromo- 2, 6-dimethylphenol.

I claim:
 1. A process to prepare a 4-HALOmethyl-3, 5-dihalo-2,6-disubstitutedphenol comprising contacting a4-methyl(substituted)phenol with a HALOgenating agnet, in an aproticorganic diluent, under conditions whereby the 4-HALOmethyl-3,5-dihalo-2, 6-disubstitutedphenol is prepared.
 2. The process of claim 1wherein the 4-HALOmethyl-3, 5-dihalo-2, 6-disubstituted phenol is of the##STR4## and the 4-methyl(substituted)phenol is of the formula ##STR5##wherein Q is separately at each occurrence in each formulaC₁₋₁₂ alkylwith the carbon bonded directly to the phenol ring selected from thegroup consisting of primary and secondary carbons, or C₁₋₁₂ generallyinertly-substituted alkyl; Q' is separately at each occurrence hydrogen,fluoro, chloro or bromo; X is separately at each occurrence fluoro,chloro or bromo; and X' is separately at each occurrence HALO,
 3. Theprocess of claim 2 wherein at least one q' is fluoro, chloro or bromo.4. The process of claim 3 wherein the HALOgenating agent is a molecularHALOgen contacted with the 4-methyl(substituted)phenol in a mole ratioof molecular HALOgen to 4-methyl(substituted)phenol of about 5:1 orlower.
 5. The process of claim 4 wherein the aprotic organic diluent isa haloalkane.
 6. The process of claim 5 wherein the HALOgenating agentis elemental bromine.
 7. The process of claim 6 wherein Q is methyl. 8.The process of claim 7 wherein conversion of the4-methyl(substituted)phenol is about 65 percent or above, by weight, andselectivity of the converted product to the 4-HALOmethyl-3, 5-dihalo-2,6-disubstitutedphenol is about 90 percent or above, by weight.
 9. Theprocess of claim 8 wherein Q' is bromo.
 10. The process of claim 9wherein the selectivity is about 95 percent or above.
 11. The process ofclaim 2 wherein Q' is hydro.
 12. The process of claim 11 wherein theHALOgenating agent is a molecular HALOgen contacted with the4-methyl(substituted)phenol in a mole ratio of about 7:1 or lower. 13.The process of claim 12 wherein the aprotic organic diluent is ahaloalkane, and X is HALO.
 14. The process of claim 13 wherein theHALOgenating agent is elemental bromine, and the HALO is bromo.
 15. Theprocess of claim 14 wherein Q is methyl.
 16. The process of claim 15wherein conversion of the 2, 4, 6-trimethylphenol is about 65 percent orabove, by weight, and selectivity of the converted product to4-bromomethyl-3, 5-di-bromo-2, 6-dimethylphenol is 90 percent or above,by weight.
 17. A process to prepare 4-bromomethyl-3, 5-dibromo-2,6-dimethylphenol comprising contacting 2, 4, 6-trimethylphenol with abrominating agent in an aprotic organic diluent under conditions wherebythe 4-bromomethyl-3, 5-dibromo-2, 6-dimethylphenol is prepared.
 18. Theprocess of claim 17 wherein the brominating agent is elemental bromine;the aprotic organic diluent is a -haloalkane; conversion of 2, 4,6-trimethylphenol is 50 percent or above, by weight, and selectivity tothe 4-bromomethyl-3, 5-dibromo-2, 6-dimethylphenol is about 95 percentor above, by weight.
 19. The process of claim 18 wherein the conversionis 60 percent or above.
 20. The process of claim 17 wherein thehaloalkane is bromochloromethane, and upon recrystallization inmethylene chloride, the purity of the 4-bromomethyl-3, 5-dibromo-2,6-dimethylphenol is 99 percent or greater.
 21. A process to prepare a4-methyl-3, 5-dihalo-2, 6-disubstitutedphenol comprising contacting a4-methyl(substituted)phenol with a halogenating agent, in an aproticorganic diluent, under conditions whereby the 4-methyl-3, 5-dihalo-2,6-disubstitudphenol is prepared.
 22. The process of claim 21 wherein the4-methyl-3, 5-dihalo-2, 6-disubsitiuted phenol is of the formula##STR6## and the 4-methyl(substituted)phenol is of the formula ##STR7##wherein Q is separately at each occurrence in each formulaC₁₋₁₂ alkylwith the carbon bonded directly to the phenol ring selected from thegroup consisting of primary and secondary carbons, or C₁₋₁₂ generallyinertly-subsitiuted alkyl; Q' is hydrogen, fluoro, chloro or bromo;provided that at least one Q' is hydrogen, and X is separately at eachoccurrence fluoro, chloro or bromo.
 23. The process of claim 22 whereinthe halogenating agent is a molecular HALOgen contacted with the4-methyl(substituted)phenol in a mole ratio of molecular HALOgen to4-methyl(substituted)phenol of about 1:1 to about 2:1; the aproticorganic diluent is a haloalkane, and the yield of the 4-methyl-3,5-dihalo-2, 6-disubstitutedphenol is about 65 percent or above byweight.
 24. The process of claim 23 wherein Q is methyl, and themolecular HALOgen is elemental bromine.
 25. The process of claim 24wherein Q' is hydro; X is bromo, and the haloalkane isbromochloromethane.